EP3526161A1 - Process for producing compressed hydrogen in a membrane reactor and reactor therefor - Google Patents
Process for producing compressed hydrogen in a membrane reactor and reactor thereforInfo
- Publication number
- EP3526161A1 EP3526161A1 EP17791317.5A EP17791317A EP3526161A1 EP 3526161 A1 EP3526161 A1 EP 3526161A1 EP 17791317 A EP17791317 A EP 17791317A EP 3526161 A1 EP3526161 A1 EP 3526161A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- membrane
- zone
- hydrogen
- reactor
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
- B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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Definitions
- This invention relates to a process for obtaining and compressing hydrogen from a hydrocarbon source.
- the invention uses a hydrogen transport membrane to separate hydrogen from its source and create hydrogen pressure on the permeate side of the membrane.
- An electric field is applied to the membrane to encourage proton transport and Joule heating during the application of the electric field can be used to supply heat for a dehydrogenation process, e.g. steam reforming of methane.
- Hydrogen can be produced from steam methane reforming (SMR), following the equation:
- the drawback for the Pd-SMR is the significant partial pressure difference of H 2 needed across the membrane, pH 2 (retanate) > pH 2 (permeate).
- the driving force for hydrogen transport is the chemical potential gradient of hydrogen across the membrane. When the hydrogen partial pressure in the retanate is low, high hydrogen recovery will be challenging.
- Pd-SMR is restricted by temperature. If operated above 500-600 °C failures have been seen due to embrittlement and coke poisoning;
- Example of such a membrane is the LaWOi 2 -LaCr0 3 based composite described in PCT/EP2014/060708. Although this composite has lower permeability it can be operated at higher temperatures compared to the Pd-SMR; the mechanical and chemical stability is also higher.
- this membrane can produce the heat in-situ if operated with an oxygen containing sweep gas; the permeated hydrogen will react with oxygen and produce steam and heat.
- the SMR process can be operated autothermally.
- the oxygen containing sweep will also provide the necessary driving force for the permeation.
- a portion of the permeated hydrogen will be consumed in the reaction with oxygen and thereby decrease the hydrogen recovery.
- the hydrogen recovery will be limited by the partial pressure of hydrogen content in the sweep gas.
- the operating pressures is high enough to cause local plastic deformation around trapped hard particles leaving residual stresses that reduce the fatigue life of the diaphragm.
- electrochemical hydrogen compressors will increase the reliability/availability over mechanical compressors as they operate without any moving parts. There remain challenges in designing these electrochemical compressors, such as their energy efficiencies.
- thermodynamically limited process towards higher conversion towards the desired product
- the membrane reactor comprises a pressure regulator at said product outlet from said second zone so that, in operation, the partial pressure of hydrogen in the second zone is higher than the partial pressure of hydrogen in the first zone.
- the membrane reactor comprises a pressure regulator at said product outlet from said second zone so that, in operation, the partial pressure of hydrogen in the second zone is higher than partial pressure of hydrogen in the first zone; and wherein joule heating which occurs during the application of the electric field over said hydrogen transport membrane is used to heat the first zone.
- the energy required to heat the first zone to the reaction temperature is derived exclusively from joule heating.
- the gas added to the first zone is ideally hydrocarbon and water.
- first zone separated by a membrane electrode assembly from a second zone, said first zone having a gas inlet and a product outlet and said second zone having a product outlet wherein said product outlet is provided with a pressure regulator;
- a power source adapted to pass an electric field over the membrane electrode assembly
- membrane electrode assembly comprises, in the following layer order:
- b is 0-0.45;
- c 0.1-0.5
- the process of the invention takes place in a membrane reactor in which the membrane separates a first zone and a second zone.
- the first zone may be provided with a catalyst to encourage the dehydrogenation process.
- the second zone comprises an outlet for the gas that passes through the membrane.
- the outlet comprises a pressure regulator that enables compression of the hydrogen within the second zone.
- the reactant is introduced into the first zone and an electric field is applied across the membrane. This encourages the hydrogen that forms to dissociate into protons to pass through the membrane.
- the heat generated by the passing of current is used to encourage the endothermic reforming reaction.
- Methane is dehydrogenated according to the equation:
- any alkene formed may dimerise or trimerise under the conditions in the reactor to form, for example benzene.
- the conversion of reactant achieved in this type of dehydrogenation process is preferably at least 15 wt%, preferably at least 20 wt%, e.g. 25 wt% or more.
- the selectivity is preferably at least 70 wt%, preferably at least 85 wt%, e.g. close to 100 wt%. This means that the formed dehydrogenated product is at least 95 wt% pure, i.e. there are almost no impurities present at all, except unconverted reactant and hydrogen.
- the gas being dehydrogenated is a mixture of alkanes and water, i.e. as in steam reforming with subsequent water-gas-shift reaction.
- Methane is reformed according to the following equation:
- the overall reforming reaction (steam reforming + water-gas-shift) is endothermic, and conventionally heat can be supplied by heat transfer through the membrane from the exothermic reaction between permeated hydrogen and sweep air.
- heat is preferably supplied via ohmic losses and hence joule energy as discussed further below.
- the membrane enables heat management within the system. Further, compared to using complex metal membranes or unstable perovskites of the prior art, the proton conducting membrane of this invention is stable even in chemically harsh conditions at high temperatures.
- the first zone of the membrane reactor contains water (steam) in addition to a hydrocarbon substrate.
- the reaction products at the outlet of the first zone include CO and/or C0 2 . These do not pass through the membrane and can be extracted from the first zone.
- the feed gas is a mixture of methane and steam in a 1 :2 to 1 :3 molar ratios.
- a current is applied across the membrane in order to encourage transport of hydrogen across the membrane.
- the heat emitted from the ohmic losses in the membrane operation can be used as reaction heat for the hydrocarbon reforming reaction. So the membrane offers ohmic resistance generating heat. That heat can be converted into chemical energy by heating the hydrocarbon and hence generating hydrogen.
- steam reforming is highly endothermic. Note also, that the electrochemical compression of hydrogen will generate heat in itself. It is important therefore that steam reforming is endothermic as the reaction in first zone act as a heat sink for the heat generated ohmically across the membrane and during compression.
- Hydrogen is extracted from the retenate side of the membrane using an external bias allowing for direct compression of the hydrogen gas.
- the process is not dependent on z/pH 2 across the membrane. Additionally, high hydrogen recovery can be obtained as the removal of hydrogen from the retenate side of the membrane shifts the shift reaction towards C0 2 .
- a membrane electrode assembly of 18.9 cm 2 with an area specific resistance (ASR) of 0.8 ⁇ cm 2 operating at a current density of 328 mA/cm 2 will emit 2.7 W.
- a bundle of 215 tubes will generate 14 kWh during 24h operation. This heat will balance the heat required to reform 6 Nm 3 of CH 4 at a conversion of 98 %.
- the reactor is provided with a hydrogen transport membrane which selectively allows hydrogen, in the form of protons, to leave the first zone of the reactor through the membrane but does not allow the starting material hydrocarbon, water or any products to pass through.
- the membrane may be called a protonic membrane herein.
- the membrane separates the first reaction zone in which a dehydrogenation process takes place (i.e. in which the feed and, if present, dehydrogenation catalyst come together) from the second zone which will contain hydrogen which passes through the membrane and any means desired to remove that hydrogen.
- the hydrogen transport membrane has some oxygen ion transport properties as well. If the permeate sweep comprises an oxygen containing gas, there will be a gradient to allow oxygen to transport from the permeate side to the reactor chamber (first zone), i.e. across the membrane. A small amount of oxygen in the reactor chamber is favourable to reduce coke formation.
- Such an oxygen containing material can be water (steam).
- the hydrogen transport membrane must be of a material that can selectively transport hydrogen in ionic form as protons. It is preferred if the membrane material is chemically inert and stable at temperatures between 500 °C and 1000 °C in atmospheres containing gases such as alkanes, water, hydrogen and C0 2 .
- the membrane material should not promote carbon deposits in the reactor, which typically means that the material should have very low tendency towards carbon uptake, should be of a basic nature and also should have a surface that does not catalytically promote activation of alkanes, in particular methane.
- the membrane material used in the hydrogen transport membrane comprises a mixed metal oxide.
- the transport membrane will possess a proton conductivity of at least 1 x 10 "3 S/cm.
- the proton conductivity of the membrane of the invention is preferably at least 1.5 x 10 "3 S/cm, especially at least 5 x 10 "3 S/cm.
- the membrane of the invention should an oxygen transport number of 0.001 to 0.5, such as 0.01 to 0.2, preferably between 0.05 and 0.1.
- a range of mixed metal oxides may be suitable, including acceptor doped perovskites (such as Y-doped BaZr0 3 and Y-BaCe0 3 ).
- Preferred membrane materials therefore include pervoskites according to the general formula (IV)
- element B can represent more than one element, such as Zr and Ce.
- element B' can represent more than one element, such as Y and Yb.
- A, Zr, Ce, Acc and O wherein A is Ba, Sr or Ca or a mixture thereof; and Acc is a trivalent transition metal or trivalent lanthanide metal such as Y, Yb, Pr, Eu, Pr, In, or Sc or a mixture thereof.
- a preferred oxide comprises a mixed metal oxide of formula (I)
- b is 0-0.45;
- c 0.1-0.5
- Acc is a trivalent transition metal or lanthanide metal, such as Y, Yb, Pr, Eu, Pr, In, or Sc or a mixture thereof;
- y is a number such that formula (I) is uncharged, e.g. y is 2.75 ⁇ y ⁇ 2.95.
- A is Ba. It is preferred if Acc is Y or Yb or a mixture thereof, especially Y.
- the membrane comprises a mixed metal oxide of formula (IF) or ( ⁇ ")
- b is 0-0.45;
- c 0.1-0.5
- y is a number such that formula (I) is uncharged, e.g. y is 2.75 ⁇ y ⁇ 2.95. Where b is 0 there are no Ce ions and the formula reduces to:
- c 0.1-0.5
- y is a number such that formula (I) is uncharged, e.g. y is 2.75 ⁇ y ⁇ 2.95.
- a preferred ceramic comprises ions of Ba, Ce, Zr, Y and O.
- a highly preferred ceramic mixed metal oxide is of formula BaZro. 7 Ceo. 2 Yo.i0 3 _6.
- b+c sums to 0.1 to 0.5, such as 0.2 to 0.4.
- b is 0.1 to 0.4, such as 0.15 to 0.3, e.g. 0.2.
- c is 0.05 to 0.2.
- the ceramic material of the membrane adopts a perovskite crystal structure.
- the metal ions required to form the ceramic mixed metal oxide that forms the membrane layer can be supplied as any convenient salt of the ion in question.
- a sintering process is required. During the sintering process, the salts are converted to the oxide so any salt can be used. The amount of each component is carefully controlled depending on the target end mixed metal oxide.
- Suitable salts include sulphates, nitrates, carbonates and oxides of the ions.
- the use of sulphates is preferred for the alkaline earth metal component, especially BaS0 4 .
- the use of Ce0 2 is preferred for the cerium ion source.
- the use of Zr0 2 is preferred as the Zr source.
- the use of oxides is preferred for the Acc ion source.
- Y 2 0 3 is preferred as the Y ion source.
- Particles of the reactant precursor materials can be milled to form a powder mixture.
- the membrane layer may have a thickness of 1 to 500 micrometers, such as 10 to 150 micrometres. Membranes having thickness in the lower end of the range will require a structural support, while membranes with thickness in the higher end of the indicated thickness range may be "self-supported".
- the reactants needed to make the membrane layer are prepared as a slurry in an aqueous or non aqueous solvent (such as an alcohol).
- an aqueous or non aqueous solvent such as an alcohol
- the use of water is preferred.
- the relative amounts of the reactants can be carefully measured to ensure the desired mixed metal oxide stoichiometry. Essentially all the metal oxide present becomes part of the sintered membrane body and all other components are removed thus the amounts of each component required to develop the desired stoichiometry can be readily calculated by the skilled person.
- the slurry used to make the membrane may comprise other components present to ensure the formation of membrane.
- Such components are well known in the art and include binders, rheology modifiers, dispersants and/or emulsifiers or other additives to ensure that the support forms and remains solid and intact until the sintering process. Additives therefore act as a kind of adhesive sticking the metal salt particles together to form a layer.
- Suitable additive compounds include ammonium polyacrylate dispersant and acrylic emulsions.
- the content of additive such as emulsifier/dispersant may be between 0 to 10 wt%, such as 1 to 5 wt% of the mixture as a whole.
- Suitable binders would be methyl cellulose, acrylic emulsions, and starches. The content of such binders may be between 0 to 10 wt% such as 1 to 5 wt% of the mixture as a whole.
- Water is the preferred solvent and may form 5 to 20 wt% of the slurry used to form the membrane.
- the metal components required to form the composite may form 50 to 80 wt% of the slurry.
- This slurry can be extruded, applied to a mould etc to form the membrane and subsequently dried to leave a solid but unsintered green body as a precursor to the membrane layer.
- any additives present are preferably organic as these will decompose during the sintering process.
- the green layers described herein are precursors of the actual membrane. The membrane is formed upon sintering, described in detail below.
- Electrodes may be added to operate the membrane. Preferred electrodes, which are exposed to the first zone of the reactor, should have following characteristics:
- Porous microstructure to allow gas diffusion of 3 ⁇ 4 to and from triple phase boundaries and avoid concentration polarization due to accumulation of larger hydrocarbon molecules or steam
- the electrode can be a single phase or composite with multiple phases.
- Some potential candidate materials include the following groups:
- Metals/metal alloys such as Ni, Fe, Pt and Pd alloys
- Mixed metal oxides such as Lai_ x Sr x Cri_ y Mn y 03
- the electrode has catalytic properties for the steam methane reforming reaction.
- Such materials are:
- the second electrode not exposed to the first zone in the membrane reactor may be selected from a wider range of materials known to those skilled in the art.
- the electrodes required form part of a membrane electrode assembly (MEA) comprising two electrode layers and a membrane layer (or electrolyte layer).
- MEA membrane electrode assembly
- the electrodes in this embodiment may be of the same composition, especially using a material that both exhibits activity for steam reforming and hydrogen disassociation/association.
- a material may be Ni. This embodiment is described in more detail below.
- the hydrogen transport membrane assemblies can be fabricated with such techniques generally known to those skilled in the art of fuel cells and inorganic gas separation membranes.
- the membrane of the invention is self-supporting however, it is within the scope of the invention to use a support.
- the support should be inert, porous and capable of withstanding the conditions within the reactor.
- the support also forms an electrode.
- Porous Chemically compatible with the membrane - does not react to form a secondary insulating phase
- Mechanically compatible with the membrane - thermal expansion coefficient should preferably match that of the membrane.
- the support will be an inert metal oxide such as an alkali metal oxide or silica or alumina. Such supports are well known in this field.
- the particle size in the support should be greater than the particle size in the membrane, e.g. at least 200 nm higher. Supports may be 2-300 ⁇ to 1 mm or more in thickness.
- the design of the support material depends on the design of the whole reactor.
- the membrane, and hence any support will be planar or tubular.
- the term tubular may be used herein to designate a membrane that is a hollow cylinder with two open ends, or alternatively it may be a plurality of smaller channels forming a "honeycomb structure" or it can take the shape of a "test tube", i.e. a cylinder with hemispherical end portion but open at the other end.
- porous support tubes can be extruded. Both thermoplastic and water based extrusion processes can be used. The support is then heat treated to yield the desired mechanical strength.
- the support material can be tape cast, also followed by heat treatment to yield the desired mechanical strength.
- a slurry of the material is typically spread evenly onto a flat horizontal surface by means of a doctor blade. After drying, the thin, film formed can be removed, cut to the desired shape and fired.
- an ink of the desired support material can be produced either using water as a solvent or an organic solvent, optionally as well as stabilizing agents.
- a pore filler material is often used, e.g. carbon black.
- the ink can then be tape cast or extruded.
- the support is subsequently fired to a desired firing temperature, such as 600 to 1500°C to yield mechanical robust supports with a desired porosity.
- the porous support tubes can be prepared by gel casting.
- a mould is prepared of the desired structure.
- a solution of the desired material is then prepared and poured into the mould. After the solution is gelified the mould is removed.
- the support is subsequently fired to a desired firing temperature, such as 600 to 1500°C to burn out the organic residue and to yield mechanically robust supports with a desired porosity.
- the membrane is self supported.
- the invention is multilayered and is formed from a layer of the hydrogen transport material, and two layers which act as electrodes. One or both also act as support layers.
- a supported membrane can be called a membrane electrode assembly (MEA) and comprises an anode/electrolyte/cathode configuration in which one electrode layer acts as a structural element to support mechanical loads.
- the electrode layers are porous and the electrolyte layer is dense (non porous).
- the dense layer is the hydrogen transport membrane as hereinbefore defined.
- the MEA therefore has the structure: first electrode: membrane; second electrode.
- the first electrode layer tends to be thicker than the electrolyte or second electrode layer as it supports the MEA. It is therefore preferred if the MEA does not contain a separate support layer. The MEA should be supported by the first electrode layer.
- the first electrode layer may have a thickness of 250 microns to 2.0 mm, such as 500 microns to 1.5 mm, preferably 500 microns to 1.2 mm.
- the first electrode layer is preferably produced in the green state, i.e. it is not sintered/densified before the application of the electrolyte layer thereto.
- the MEA may be in cylindrical form or planar form (or any other layered structure as required). Ideally however, the MEA is planar or cylindrical, especially cylindrical. Either anode or cathode can be present at the centre of the cylinder and the first electrode layer can be either anode or cathode.
- the method for the preparation of the first electrode layer is quite flexible.
- a mould or support may be used.
- the first electrode layer may be deposited on a cylindrical or planar supporting mould. After the layer is formed, the mould can be removed leaving the first electrode layer. Alternatively, the first electrode layer could be extruded to form a cylinder or planar support.
- the first electrode layer may be prepared by methods including extrusion, slip casting, injection molding, tape casting, wet and dry bag isopressing, and additive manufacturing.
- the length/width of the first electrode layer is not critical but may be 10 to 50 cm.
- the inner tube diameter may be 2.0 mm to 50 mm, such as 2.0 to 15.0 mm.
- inner tube diameter means the diameter is measured from the inside of the layer and excludes the thickness of the actual tube.
- the mixture used to manufacture the supporting electrode material comprises ceramic powders and optional additives such as emulsifiers, pore formers, binders, rheology modifiers etc. in order to allow the formation process.
- the first electrode is preferably produced from a slurry comprising ceramic components, binders and rheology modifiers.
- the first electrode will comprise a mixed metal oxide so the mixture used to prepare it should comprise precursors to the desired mixed metal oxide.
- a preferred mixed metal oxide is based on the combination of an alkaline earth metal such as Ba or Sr with Zr and a lanthanide such as Y. The use of Ba, Zr and Y is preferred (forming therefore a BZY type mixed metal oxide).
- the support electrode, after sintering is a BZY type material.
- the mixed metal oxide may also preferably contain Ce ions.
- the first electrode comprises ions of
- a preferred final (i.e. sintered) first electrode layer comprises a mixed metal oxide of formula (I)
- b is 0-0.45;
- c 0.1-0.5
- Acc is a trivalent transition metal or lanthanide metal such as Y, Yb, Pr, Eu, Pr, Sc or In, or a mixture thereof;
- y is a number such that formula (I) is uncharged, e.g. y is 2.75 ⁇ y ⁇ 2.95. Where b is 0 there are no Ce ions and the formula reduces to:
- y is a number such that formula (I) is uncharged, e.g. y is 2.75 ⁇ y ⁇ 2.95.
- a preferred ceramic comprises ions of Ba, Ce, Zr, Y and O.
- a highly preferred ceramic mixed metal oxide is of formula BaCeo.2Zro.7Yo.i0 3 _6. It is preferred if b+c sums to 0.1 to 0.5, such as 0.2 to 0.4.
- b is 0.1 to 0.4, such as 0.15 to 0.3, e.g. 0.2.
- c is 0.05 to 0.2.
- the ceramic material of the first electrode adopts a perovskite crystal structure.
- the ratio of Ni compound : mixed metal oxide in the composite after sintering may be 0.2 to 0.8 on a volumetric basis.
- the nickel compound(s) forms at least 50 wt% of the green electrode layer.
- the Ni component forms at least 50 wt% of the sintered electrode.
- the metal ions required to form the ceramic mixed metal oxide that forms the electrode layer can be supplied as any convenient salt of the ion in
- the salts are converted to the oxide so any salt can be used.
- the amount of each component is carefully controlled depending on the target end mixed metal oxide.
- the Ni oxide acts as a sintering aid. .
- the amount of Ni material added can also be readily calculated by the skilled person.
- the reactants and the Ni oxide needed to make the first electrode layer are prepared as a slurry in an aqueous or non aqueous solvent (such as an alcohol).
- an aqueous or non aqueous solvent such as an alcohol
- the use of water is preferred.
- the relative amounts of the reactants can be carefully measured to ensure the desired mixed metal oxide stoichiometry and the desired Ni content in the final product after sintering. Essentially all the metal oxide/NiO present becomes part of the sintered electrode body and all other components are removed thus the amounts of each component required to develop the desired stoichiometry can be readily calculated by the skilled person.
- the slurry used to make the first electrode layer may comprise other components present to ensure the formation of an electrode layer.
- Such components are well known in the art and include binders, rheology modifiers, dispersants and/or emulsifiers or other additives to ensure that the electrode support forms and remains solid and intact until the sintering process. Additives therefore act as a kind of adhesive sticking the metal salt particles together to form a layer.
- Suitable additive compounds include ammonium polyacrylate dispersant and acrylic emulsions.
- the content of additive such as emulsifier/dispersant may be between 0 to 10 wt%, such as 1 to 5 wt% of the mixture as a whole.
- Suitable binders would be methyl cellulose, acrylic emulsions, and starches. The content of such binders may be between 0 to 10 wt% such as 1 to 5 wt% of the mixture as a whole.
- This slurry can be extruded, applied to a mould etc as discussed above to form the first electrode and subsequently dried to leave a solid but unsintered green body as a precursor to the composite first electrode layer.
- any additives present are preferably organic as these will decompose during the sintering process.
- the green layers described herein are precursors of the actual electrode. The electrode is formed upon sintering.
- the second electrode typically has a similar structure to that of the first electrode. It is ideally therefore a composite of a mixed metal oxide and Ni oxide. Any method can be used to apply the second electrode layer to the electrolyte layer. It will be appreciated that these two layers should be adjacent without any intermediate layer. Methods include dip coating, spray coating, hand wash, pulsed laser deposition, physical vapor deposition, and screen printing.
- the second electrode layer may have a thickness of 20 to 400 microns, such as 30 to 100 microns.
- the second electrode layer need not cover the whole of the electrolyte layer.
- the dimensions of the second electrode layer can be controlled by the person skilled in the art.
- the second electrode layer is preferably provided as a green ceramic slurry.
- the weight fraction of metallic powders to spray vehicle is preferably between 30 and 85% by weight, preferably from 40 to 76%.
- the solvent for the second electrode slurry may be organic or aqueous but is preferably aqueous so as to minimize re-dissolution of the electrolyte layer and/or swelling of the electrolyte layer both of which would lead to catastrophic failure of the membrane prior to further processing.
- the ceramic compounds used to form the second electrode layer are ideally mixed with additives including emulsifiers, rheology modifiers, binders and so on to ensure a good layer application to the electrolyte layer.
- the viscosity of the slurry is controlled to aid deposition.
- the viscosity required is a function of the nature of the application technique.
- slurries may have a viscosity of 10 to 30 cP as measured using a LV2 spindle at 60 rpm on a Brookfield viscometer. Being an aqueous system, the viscosity can be easily adjusted by the use of polyionic dispersing agents.
- Such dispersants can be polyacrylate and polymethacrylate salts and lignosulfonates, with ammonium polyacrylate (e.g., Duramax D-3005 or Darvan 821 A) being preferable.
- a dip coating slurry can be prepared containing approximately a) 50 wt% of a mixture comprising 75 to 95 wt % electrode powders, 2 to 3 % methylcellulose binder, up to 2 % starch, up to 2 % plasticizer, up to 2 % dispersant; and b) 50 wt % water.
- the second electrode after sintering, is a composite of formula Ni-AZr a _b- c CebAcc c 03- y Awhere the ratio of Ni-AZr a _b- c CebAcc c 03-y is 0.2 to 0.8 on a volumetric basis and the variables are as herein before defined for first electrode layer.
- the second electrode after sintering, is a composite of formula Ni-AZr a _b- c CebAcc c 03- y where the weight ratio of Ni:AZr a _b_ c CebAcc c 0 3 - y is 0.2 to 0.8 and the variables are as herein before defined for first electrode layer.
- the porosity of the Ni-cermet can be achieved with a similar manner as the 1 st electrode.
- the porosity is achieved by reducing NiO to Ni under reducing conditions at 500-1000 °C.
- the solvent used to deposit the outer electrode is different from the solvent used to deposit the membrane layer. This is important as we don't want the subsequent electrode deposition step to dissolve any of the binders used in the membrane formation step.
- water is employed as the solvent for outer electrode deposition and an ester as the solvent for the spray coating of the membrane.
- Additives can be added to the slurries used in the coating process to adjust the solubility of the membrane layer/electrode layer in organic/aqueous solvents. Sintering
- the whole assembly can be sintered.
- the whole assembly is subject to thermal heat treatment to firstly remove organic components and any water and secondly to densify the assembly. It may be that the heat treatment process is effected in stages.
- Spray deposition methods e.g. ultrasonic spray deposition (USD);
- the membrane is preferably deposited on a porous support using a screen printing technique.
- the process of the invention requires that the starting material is fed in the reactor.
- the temperature of the feed is such that the materials are fed as gases but typically, the feed will be heated to have the same temperature as the reactor.
- the process within the reactor is normally operated at high temperatures of 300°C to 1000°C, preferably 400°C to 800°C.
- the pressure within the reactor may range from 0.5 to 50 bar, preferably 5 bar to 25 bar.
- Hydrogen is generated during the dehydrogenation reaction and the amount of hydrogen removed from the reactor via the transport membrane can be manipulated depending on how the user wants the process to be run.
- the pressure in the second zone increases.
- the partial pressure of hydrogen in the second zone is higher than the partial pressure of hydrogen in the first zone.
- the pressure in the second zone is at least 2x, such as at least 5x such as at least 15x the pressure in the first zone. Pressures up to 20x or less are possible.
- the partial pressure of hydrogen in the first zone may be 1-70 bar, or more preferred 5-30 bar or most prefererd 10-20 bar.
- the reactor is provided with a pressure regulator at the gas outlet within the second zone.
- This pressure regulator enables control over the pressure with the second zone by preventing hydrogen that has passed across the membrane from escaping the second zone.
- the pressure of hydrogen in the second zone is higher than the pressure of hydrogen in the first zone and can be controlled via the pressure regulator. This is clearly illustrated in figure 1.
- the pressure regulator can be used to ensure a particular pressure is achieved within the second zone. Suitable pressures within the second zone are 2 to 700 bars, such as 10 to 350 bars, e.g. 20 to 100 bars.
- Joule heating also known as ohmic heating or resistive heating, is the process by which the passage of an electric current through a conductor releases heat.
- the ohmic loss during the operation of the membrane will cause Joule heating.
- the heat generated in this process can be used to provide the heat required for the reforming process.
- the reactor used in the present process may employ a dehydrogenation catalyst to encourage the dehydrogenation reaction. Any dehydrogenation catalyst capable of achieving the desired process can be used.
- the dehydrogenation catalyst may be integrated in the catalytic membrane reactor as a packed fixed bed, as a fluidized bed, by deposition on the membrane wall, by being a part of or the same as an electrode, or in other way.
- the dehydrogenation catalyst is preferably a porous catalyst but it should ideally have some electron and proton conductivity as these species may need to be transported through the catalyst on the membrane.
- the one suitable catalyst is a H-ZSM5 or MCM-22 zeolite with an active metal with reported activity in the order Mo > W > Ga > Fe > V > Cr to form aromatic products.
- the most suitable catalysts include metals of the first row of transition metals such as Ni, Fe, Pt, Ag, Pd and their alloys. These can be supported on alkali metal oxides with suitable examples Cr0 2 , Mo0 3 and V 2 0 5 . or be a part of the electrode.
- any of the above mentioned catalysts for methane is applicable, but preferred catalysts include alumina supported Ga 2 0 3 , Cr0 2 , Mo0 3 and V 2 0 5 such as Cr0 2 , Mo0 3 and V 2 0 5 .
- the catalyst is a part of the electrode.
- the catalyst material functions both as the electronic conductor for the electrode and as a catalyst for the dehydrogenation reaction.
- the deposition will be as that described for electrode fabrication.
- the catalyst will be deposited on the membrane. This will be achieved by techniques such as dip coating or impregnation, where the catalyst is dispersed in a solution. The membrane is then heat treated so that the catalyst is adhered to the membrane surface. The deposition can also be achieved by growing the catalyst directly on the membrane by a crystal growth technique.
- a second embodiment includes a reactor where the catalyst is freely lying on top of, or in front of the membrane.
- the catalyst can be in the form of powder with tailored particle size. The catalyst is not adhered to the membrane.
- the catalyst can therefore easily be exchanged if it needs to be regenerated.
- no catalyst is used at all. In some embodiments, the material used in the membrane has sufficient catalytic activity that no further catalyst is needed. Catalytic membrane reactor
- any reactor design can be used, however preferred reactor designs are flow-type fixed bed, fluidized bed and wash-coated designs. It is important therefore that there is flow from inlet to outlet in the first zone of the reactor.
- One advantageous design utilises a reactor within which there is a tubular transport membrane. Between the reactor walls and the tubular membrane is an optional bed of dehydrogenation catalyst. This forms the first zone in the reactor. This bed need not extend the whole length of the reactor but it may. Alternatively, the first zone of the reactor is inside the tube where the catalyst is preferably located.
- water and alkane gases are fed into the first zone.
- the gases are fed into the inside of the tube, if that is preferred.
- Dehydrogenation occurs on contact between the reactants and any catalyst thus forming hydrogen.
- Hydrogen gas generated passes through the membrane and into the second zone of the membrane which is dependent on where the catalytic reaction occurs.
- FIGURES Figure 1 shows the increasing pressure within the membrane reactor during steam reforming.
- FIG. 2 is a general schematic of a membrane electrode assembly (MEA) showing an anode at which reactions occur that generate electrons, a cathode at which reactions occur that consume electrons, and an electrolyte which conducts ions but is insulating towards electrons.
- MEA membrane electrode assembly
- Fig. 5 shows the support layer (1) with membrane layer (2) and outer electrode layer 3.
- the embodiment shown has a counter-current gas flow.
- This configuration has a similar hydrogen pressure gradient ⁇ in the two end segments.
- the first segment is located at the inlet of the reactant gas.
- the hydrogen concentration will be highest at this point, while the oxygen content in the purge gas will be the lowest.
- the hydrogen pressure will be at the lowest point, while the oxygen pressure will be at the highest.
- the pressure gradient in the two ends will be approximately equal, which is also true for the part between the two ends. This will ensure a homogeneous dehydrogenation along the membrane, which furthermore will stabilize the conversion towards carbon formation. In this way a constant thickness of the membrane can be used throughout the reactor.
- a tubular asymmetric membrane of 60 wt.% Ni-BaZro.7Ceo. 2 Yo.i03_6 (BZCY72) support with a 30 ⁇ dense membrane was synthesized using a reactive sintering approach (Coors et al. Journal of Membrane Science 376 (2011) 50-55). Precursors of BaS0 4 , Zr0 2 , Y2O3 and Ce0 2 were mixed in stoichiometric amounts (metal basis) together in a Nalgene bottle on ajar roller for 24 h. The material was dried in air and sieved through a 40 mesh screen. This forms a precursor mixture.
- Green tubes were extruded using a Loomis extruder.
- the extruded tubes were then dried and spray coated with the precursor mixture after drying. After a second drying step the tubes were dip coated in a solution of the previous second portion (containing NiO).
- the tubes were co-fired by hang-firing in air at 1600°C for 4 h. This process creates an internal NiO-BZY support layer with dense membrane layer and outer NiO-BZY layer.
- the sintered tubes were then treated in a hydrogen mixture (safe gas) at 1000°C to reduce the NiO to Ni and give the necessary porosity in anode support structure and outer cathode.
- Dimensions of the cell tube are ⁇ 25 cm long with an outer diameter of ⁇ 10 mm, an inner diameter of ⁇ 9.8 mm and a membrane thickness of ⁇ 30 ⁇ .
- the anode support structure consisting of the 60 wt.% -BZCY72 provides sufficient catalytic activity
- the reactor consists of a 1 " metallic outer tube (800 HT).
- the ceramic tube above was mounted on a membrane tube fitting with a o-ring (Kalrez) seal and placed inside the outer tube.
- Inner gas tube and current collector consisted of at Ni-tube (O.D. 4.6 mm). To ensure contact with the support, Ni wool was put into the end of the tube. The temperature was monitored with 3 thermocouples, two outside the reactor at heights corresponding to the top and bottom of the electrode, and one inside ceramic tube at a height corresponding to the top of the electrode. For cathode current collector Cu wire was wrapped around the electrode.
- Gas analysis was performed using a micro GC (Model 490, Varian) measuring the concentrations of He, H 2 , CH 4 , CO and C0 2 in the product and sweep outlet gas lines.
- the anode support structure consisting of the 60 wt.% -BZCY72 provides sufficient catalytic activity Reactor and setup
- the reactor consists of a 1 " metallic outer tube (800 HT).
- the segmented ceramic tube on riser was mounted with Swagelok fittings seal and placed inside the outer tube.
- Inner gas tube and current collector consisted of at Ni-tube (O.D. 4.6 mm). To ensure contact with the support, Ni wool was put into segment A. The temperature was monitored with 3 thermocouples, two outside the reactor at heights
- the reactor was operated at 800 °C using the reactor and membrane electrode assembly as described above.
- a gas mixture consisting of 28% CH 4 , 17% H 2 and 55% H 2 0 was fed to the first zone where a reforming reaction occurs to convert methane and steam to hydrogen to thermodynamic equilibrium.
- An external electric field of 5 A was applied to the membrane.
- a back pressure regulator at the outlet of second zone was adjusted so that the pressure increased in a step-wise manner.
- the continuous transport of hydrogen through the membrane allows for a continuous increase in pressure as shown in Fig. 1.
- a total pressure difference of 11 bar was obtained.
- a membrane electrode assembly of 18.9 cm 2 with a area specific resistance (ASR) of 0.8 ⁇ cm 2 operating at a current density of 328 mA/cm 2 will emit 2.7 W.
- a bundle of 215 tubes will generate 14 kWh during 24h operation. This heat will balance the heat required to steam reform 6 Nm 3 of CH 4 at a conversion of 98 %.
Abstract
Description
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US11661660B2 (en) * | 2017-03-16 | 2023-05-30 | Battelle Energy Alliance, Llc | Methods for producing hydrocarbon products and protonation products through electrochemical activation of ethane |
US11421330B2 (en) * | 2017-03-16 | 2022-08-23 | Battelle Energy Alliance, Llc | Methods for carbon dioxide hydrogenation |
US11668012B2 (en) * | 2017-12-11 | 2023-06-06 | Battelle Energy Alliance, Llc | Methods for producing hydrocarbon products and hydrogen gas through electrochemical activation of methane |
US11731920B2 (en) * | 2018-08-06 | 2023-08-22 | Battelle Energy Alliance, Llc | Methods for co-producing hydrocarbon products and ammonia |
GB202103454D0 (en) * | 2021-03-12 | 2021-04-28 | Coorstek Membrane Sciences As | Ammonia dehydrogenation |
WO2023277964A1 (en) * | 2021-06-30 | 2023-01-05 | Coors W Grover | Porous nibzy supports for hydrogen separation membranes |
WO2023227313A2 (en) * | 2022-05-23 | 2023-11-30 | Metharc Aps | New electrochemical reactor design |
JP2024009392A (en) * | 2022-07-11 | 2024-01-23 | ヤンマーホールディングス株式会社 | Ammonia decomposition system, internal combustion engine system, and ammonia decomposition method |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5900031A (en) | 1997-07-15 | 1999-05-04 | Niagara Mohawk Power Corporation | Electrochemical hydrogen compressor with electrochemical autothermal reformer |
US5908713A (en) | 1997-09-22 | 1999-06-01 | Siemens Westinghouse Power Corporation | Sintered electrode for solid oxide fuel cells |
US6168705B1 (en) | 1998-09-08 | 2001-01-02 | Proton Energy Systems | Electrochemical gas purifier |
US6296687B2 (en) * | 1999-04-30 | 2001-10-02 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources | Hydrogen permeation through mixed protonic-electronic conducting materials |
NL1014284C2 (en) | 2000-02-04 | 2001-08-13 | Stichting Energie | A method of manufacturing an assembly comprising an anode-supported electrolyte and a ceramic cell comprising such an assembly. |
AU2001274926A1 (en) | 2000-05-22 | 2001-12-03 | Acumentrics Corporation | Electrode-supported solid state electrochemical cell |
US20070246363A1 (en) * | 2006-04-20 | 2007-10-25 | H2 Pump Llc | Integrated electrochemical hydrogen compression systems |
US20080023322A1 (en) * | 2006-07-27 | 2008-01-31 | Sinuc Robert A | Fuel processor |
JP5071720B2 (en) | 2008-02-19 | 2012-11-14 | 学校法人玉川学園 | Hydrogen supply device |
WO2009152255A2 (en) * | 2008-06-10 | 2009-12-17 | University Of Florida Research Foundation, Inc. | Proton conducting membranes for hydrogen production and separation |
WO2009157454A1 (en) | 2008-06-27 | 2009-12-30 | 国立大学法人 鹿児島大学 | Electrochemical reactor and fuel gas manufacturing method using the same |
KR20120006499A (en) * | 2009-04-06 | 2012-01-18 | 바스프 에스이 | Method for electrochemically removing hydrogen from a reaction mixture |
WO2012036057A1 (en) | 2010-09-13 | 2012-03-22 | 住友電気工業株式会社 | Gas-decomposition device, electrochemical reaction device, and method for manufacturing said devices |
GB201309336D0 (en) | 2013-05-23 | 2013-07-10 | Protia As | Proton conducing ceramic membrage |
US10305116B2 (en) | 2014-02-12 | 2019-05-28 | Colorado School Of Mines | Cost-effective solid state reactive sintering method for protonic ceramic fuel cells |
DE102014214781A1 (en) | 2014-07-28 | 2016-01-28 | Robert Bosch Gmbh | fuel cell device |
JP6658754B2 (en) * | 2015-07-17 | 2020-03-04 | 住友電気工業株式会社 | Solid oxide fuel cell and method for producing electrolyte layer-anode assembly |
US10145016B2 (en) * | 2016-06-28 | 2018-12-04 | W. Grover Coors | Reactor-separator elements |
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US20190284048A1 (en) | 2019-09-19 |
WO2018069546A1 (en) | 2018-04-19 |
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